Capacitor memory and methods for reading, writing, and fabricating capacitor memories

ABSTRACT

An improved metal dual insulator semiconductor capacitor memory is disclosed. The memory contains a plurality of capacitor cells, each cell comprising a semiconductor substrate layer and a high conductivity layer sandwiching two insulator layers. The substrate is doped to provide avalanche breakdown in a surface depletion layer at a voltage comparable to the write voltage in the accumulation direction. The invention also provides a method of reading stored information without disturbing adjacent cells. A small variable voltage is applied across a &#34;flat-band&#34; portion of the hysteresis loop describing the voltage-capacitance relationship for the capacitor memory. A change or the absence of a change in the current through the capacitor indicates the state of the capacitor cell. Methods to fabricate the memory are also disclosed.

The Government has rights in this invention pursuant to Contract NumberAF19(628)-76-C-0002 awarded by the U.S. Department of the Air Force.

This is a continuation, of application Ser. No. 137,432, filed Apr. 4,1980, now abandoned, which is a continuation of application Ser. No.8,758 filed Feb. 1, 1979, now abandoned, which is a continuation ofapplication Ser. No. 737,165 filed Oct. 29, 1976 now abandoned.

CROSS REFERENCE TO RELATED APPLICATION

U.S. Pat. No. 4,127,900, issued Nov. 28, 1978, is a continuation-in-partof U.S. Ser. No. 737,165; U.S. Pat. No. 4,242,736, issued Dec. 30, 1980,is a division of U.S. Ser. No. 737,165.

This invention relates to semiconductor memories and in particular tometal dual insulator semiconductors in which each memory cell is acapacitor which exhibits hysteresis under a varying applied voltage.

BACKGROUND OF THE INVENTION

Semiconductor memories have been in existence for many years. Theygenerally comprise a plurality of semiconductor elements organized intoa regular cellular array which is fabricated on a single chip. Each cellis capable of storing one binary digit or one bit. Each cell maytypically be a complex structure, often including three or moreterminals to effect reading and writing of the memory.

While prior art semiconductor memories have been useful, they havegenerally consisted of relatively complex configurations. This increasesthe cost of fabrication and the size of each cell.

Dual dielectric capacitor memories have been suggested to decrease bothcost of fabrication and size. Generally however they have not succeededin providing practical structures and methods for selectively readingand writing at high speeds.

Dual dielectric capacitor memories are desirable however because theyhave the potential of providing extremely high densities in across-point addressing lattice and require zero standby power andnegligible refresh power.

At present, the generally preferred MIS capacitor memories most oftenuse a four layer metal-nitride-oxide-silicon (MNOS) structure (a dualinsulator, MIS capacitor).

As in any MIS structure, the MNOS capacitor has a capacitance which isvoltage dependent. Unlike devices having a single dielectric layer, suchas MOS capacitors, however, the capacitance versus voltage curve of theMNOS device exhibits hysteresis which arises from trapping of chargenear the interface between the two dielectric layers. This trappedcharge, whose magnitude depends on the duration and magnitude of appliedvoltage, effectively provides a bias voltage which corresponds to ashift of the voltage-capacitance relationship along the voltage axiscorresponding to a change in the "flat-band" voltage.

The charge storage in an MNOS capacitor arises from a net imbalance inthe currents which flow in the nitride and oxide layers respectively.Current flow in the oxide is primarily tunneling and current flow in thenitride is primarily Poole-Frenkel conduction. The tunneling mechanismin the oxide layer and the Poole-Frenkel conduction mechanism in thenitride layer are extremely non-linear with field. Thus small changes inthickness and dielectric fabrication conditions can lead to a highercurrent in a selected one of the two dielectrics. In one condition, ifthe oxide current exceeds the nitride current, then a positive pulse atthe metal terminal causes more electrons to enter the oxide than leavethe nitride and a net negative charge can build up at the nitride-oxideinterface. A negative pulse at the metal terminal can leave a netpositive charge at the interface. Conversely, if the nitride currentexceeds the oxide current, a positive pulse produces a positive changein charge and a negative pulse results in a negative change in storedcharge. The two modes described above are referred to as the forward (ornormal) mode (oxide current greater than nitride current) and thereverse (or complementary) mode (oxide current less than nitridecurent). A binary "1" or "0" can be associated with any two arbitrarilyselected storage states.

In practice, the straight-forward prior art approach to writing byapplying different potential polarities and thereby creating differentcharge storage states is of limited usefulness. For example, operatingin the forward mode, the speed with which the quantity of stored chargecan be changed in the positive direction at the nitride-oxide interfaceis limited to about a few milliseconds in a typical N-type MNOScapacitor cell. In contrast, the time required to build up stored chargein the negative direction in the device, in a practical system, can beas low as one microsecond or less with a thirty volt pulse. Thisstriking difference in charging times is due to the creation of a smallseries capacitance in the semiconductor substrate as a negative voltageis applied to an MNOS capacitor formed on N-type silicon. A capacitor isformed by the depletion of the silicon nearest the oxide of electronsunder the influence of the field which repels electrons from the metal.This depletion effectively places a high impedance (low capacitance) inseries with the dual dielectric capacitance (the nitride and oxidelayers). Thus, the prior art approach to writing is limited because thisseries depletion capacitance soaks up most of the voltage applied acrossthe MNOS device, leaving relatively little voltage available across thenitride-oxide layers to provide the currents needed for writing in thenegative direction. (A positive pulse applied to a P-type substrateproduces a similar effect.) After a sufficiently long time (typicallymilliseconds) an inversion layer will form causing the substatecapacitance to return to its high value and permitting dielectriccurrents to flow. The asymmetry in writing speeds for two selectedstorage states is a significant deterrent to the use of capacitors inread-write memories.

Reading or determining the state of a capacitor memory cell has, in thepast, been implemented by measuring the absolute capacitance of the celland correlating it to the capacitance-voltage hysteresis loop. The readtechniques vary but are generally characterized by applying a small ACsignal across the capacitor cell and measuring the resulting current.After adjusting the measurement for background parasitic and couplingcapacitances, the resulting measurement of current provides a measure ofthe capacitance and hence the state of the cell.

Unfortunately, measuring or "reading" the absolute capacitance of acell, is, in practice, extremely difficult because the parasitic,coupling and other capacitances inherent in a very large array tend toswamp the relatively small cell capacitance and thus provide a very lowsignal to noise ratio.

It is therefore an object of this invention to provide a high speed,capacitor memory array which can be fabricated at extremely highdensities, which can be written and read, randomly and reliably at highspeeds, and which can be manufactured with existing techniques. Otherobjects of the invention include providing a substantially non-volatilecapacitor memory using avalanche techniques to increase writing speed,providing a method of reading which does not depend on the absolutevalue of capacitance of an individual memory cell, and providing atwo-coordinate selection system which allows writing and reading at asingle cell in an array with minimum disturbance to cells sharing thesame word and digit lines.

SUMMARY OF THE INVENTION

The invention features a capacitor memory array which includes aplurality of isolated capacitor cells arranged in a rectilinear array,each capacitor cell being formed of a plurality of layers and each cellbeing described by a voltage-capacitance relationship which shifts alongthe voltage axis under the effect of applied potentials. The layersinclude a first high conductivity layer which forms part of one of aplurality of first conductivity paths. Adjacent to the first conductivelayer is a first dielectric insulating layer, which may be, for example,silicon nitride. Adjacent to the dielectric insulating layer is a seconddielectric insulating layer, for example, a thin layer of silicondioxide, which rests on a doped semiconductor substrate. Connected tothe substrate is a second high conductivity layer which forms part ofone of a plurality of second conductivity paths. The substrate is dopedto provide an avalanche breakdown condition across a depletion region ofthe substrate at a potential between 6 and 50 volts. This corresponds toa doping concentration at the substrate of between 1×10¹⁷ and 4×10¹⁵impurity atoms/cc respectively. Where a thin silicon dioxide layer isused, the silicon dioxide layer generally has a thickness less thanapproximately 50 Angstroms.

In another aspect of the invention, there is disclosed a process forwriting in a capacitor memory array having a plurality of isolatedcapacitor cells arranged in a rectilinear pattern. Each capacitor cellexhibits hysteresis under an applied potential and thus has twocapacitor states. Preferably, each capacitor cell includes a dualdielectric insulating structure as described above. The writing processfeatures the steps of first writing at a single cell or a selectedportion of the memory array by applying a potential between a firstconductivity layer and the substrate of each cell in the selectedportion of the array to be written. The magnitude and duration of thepotential are sufficient to change the charge stored in the cell orcells of the selected portion from a first state to a second state. Thiscorresponds to a change in the flat-band voltage. The charge layerresides substantially at the interface between the dielectric insulatorsand remains even after the potential is removed. When the polarity ofthe applied potential acts to drive a portion of the substrate layerinto depletion, the potential further has sufficient magnitude to effectavalanche breakdown across the depleted region of the substrate layer.Simultaneously, at least a second non-disturbing potential is applied toeach unselected cell. The magnitude and duration of the second potentialare collectively insufficient to substantially vary the charge stored inthe unselected cells. In this way, the stored charge, and hence theflat-band voltage, is substantially changed only in the selectedcapacitor cells and is substantially unaffected in the unselectedcapacitor cells.

In another aspect of the invention, a process for reading a multi-layer,dual dielectric, capacitor memory array is disclosed. The arraycomprises a plurality of isolated capacitor cells and a plurality of bitlines and a plurality of word lines connecting conductive portions ofgroups of capacitor cells. The process features the steps of applying avariable potential between the word line and bit line uniquelyidentifying a cell selected to be read, and varying the potential acrossat least a "flat-band" portion of the known voltage-capacitancerelationship for the cells. This relationship is known from theoperating parameters of the system or by experimentation. The maximummagnitude of the variable potential is maintained sufficiently small sothat the charge present in the selected cell is not substantiallychanged. The current flowing through the selected capacitor cell ismeasured versus voltage as a function of time and the state of thecapacitor cell is determined by the shape of the current versus timeprofile. In a preferred embodiment, the varying voltage is a ramp whichis varied in the direction of depletion.

DESCRIPTION OF THE DRAWINGS

Other advantages, features, and objects of the invention will appearfrom the following description taken together with the drawings inwhich:

FIG. 1 is an electrial schematic representation of a capacitor memoryaccording to the invention;

FIG. 2 is a simplified cross-sectional view of a single capacitor cell;

FIG. 3 is a perspective view of a preferred memory structure accordingto the invention;

FIG. 4 is a typical capacitance versus voltage hysteresis loop for adual insulator MIS capacitor;

FIG. 5 is an electrical schematic representation of a typical memory inthe write "0" operation;

FIG. 6 is an electrical schematic representation of a typical memory inthe write "1" operation;

FIG. 7 is a perspective view of a flip isolation structure according tothe invention;

FIG. 8 is a perspective view of a dioxide filler type isolationstructure according to the invention;

FIG. 9 is a perspective view of a junction isolation structure accordingto the invention; and

FIG. 10 is a perspective view of an amorphous silicon isolationstructure according to the invention.

DESCRIPTION OF A PREFERRED EMBODIMENT

Referring to FIG. 1, a typical memory array 8, according to theinvention, includes a plurality of capacitor cells 10 arranged in arectilinear pattern or array. Each capacitor cell 10a, 10b, . . . , 10i,is connected to one of a plurality of word lines 12a, 12b, 12c, and toone of a plurality of digit or bit lines 14a, 14b, 14c. The connectionsare made so that each pair or set or word and digit lines identifies oneand only one capacitor cell. While only nine cells are illustrated inFIG. 1, the array could be extended to any practical limit.

Each word line and each digit line can be connected independently to anyof a plurality of signals to apply selected potentials across thecapacitor cells in order to write information into the cells and to readinformation from the cells. The ability to vary the potential on theword and digit lines is illustrated schematically by switches 16a, 16b,. . . , 16f.

Referring to FIG. 2, each capacitor cell 10 consists of a plurality oflayers, a first high conductivity layer 18, a first dielectricinsulating layer 20, a second dielectric insulating layer 22, and asemiconductor substrate 24. A second high conductivity layer 26 isconnected to semiconductor substrate 24. Conductivity layers 18 and 26form part of word and digit lines 12 and 14.

Referring to FIG. 3, the preferred embodiment of the invention is aplanar array 27 of isolated MNOS capacitors, assembled on a singlemonocrystalline substrate. In this embodiment, the first highconductivity layer 18 of each cell is formed as a part of metal strips28, for example aluminum, which interconnect groups of capacitor cellsinto words. The strips 28 form the word lines 12.

Metal strips 28 overlie at each capacitor cell 10, the dielectricinsulating layer 20, which is preferably silicon nitride. Thisinsulating layer is preferably about 500 Angstroms thick. Otherdielectric insulators which have the characteristics which will bedescribed later, could also be used. The dielectric insulating layer 20overlies the thin dielectric layer 22 which is preferably a silicondioxide layer which is thermally grown on a silicon semiconductorsubstrate. The silicon dioxide layer is a thin layer, in the range ofabout 15-50 Angstroms thick. The underlying substrate 24 is preferablycomprised of an "N"-type silicon epitaxial layer which is grown on ahighly doped silicon, arsenic diffused "N+" digit or bit line 30. (AP-type substrate could also be used.) The doping concentration of thesubstrate 24 is preferably in the range 1×10¹⁷ to 4×10¹⁵ impurityatoms/cc to provide avalanche breakdown voltage in the range from 6 to50 volts as discussed below. Lines 30 correspond to bit or digit lines16 of FIG. 1. Digit lines 30 are formed in support substrate 31. Anetched cut 32 over which is grown field oxide 34 isolates the capacitorcells in a direction transverse to digit lines 30. In the preferredembodiment, the capacitor cells operate in the forward or normal modeand the oxide layer is preferably about 20 Angstroms thick. In otherapplications, it may be desirable to operate in the reverse ofcomplementary mode and the oxide layer would be on the order of 50Angstroms thick.

As noted above, the preferred type of capacitor memory cell is the MNOScapacitor. This device, as is well known in the art, provides thecapability of storing charge in the silicon nitride layer, atsubstantially the interface between the silicon nitride and the silicondioxide layers (the nitride-oxide interface). The magnitude and polarityof charge affects the capacitance of the cell as a function of voltagebecause it in effect biases the cell onto one or the other leg of ahysteresis loop which describes the voltage-capacitance relationship inthe cell. (See FIG. 4). The hysteresis phenomenon is discussed ingreater detail in connection with the write operation. The state ofcharge (magnitude and polarity) at the cell interface is used in thepresent invention to represent a binary "0" or "1" in the memory.

WRITE OPERATION

Information is stored in the capacitor memory in binary form and isrepresented by different charge states in the capacitor. The designation"1" or "0" to represent a binary digit is arbitrary as are the selectedcharge states, and for purposes of the following discussion, a "0" shallbe represented by a negative charge stored at the interface between thedielectric insulating layer and the oxide layer, whereas a "1" shall berepresented by the condition in which a positive charge is stored at theinterface. This corresponds to different capacitance values of thecapacitor cell. (Other charge states could be used, e.g., two positivecharge states or two negative charge states.)

Referring to FIG. 2, when the semiconductor memory capacitor cells arefirst fabricated, there is usually a small positive charge stored in thecell and in particular, at the interface between the dielectricinsulators. In this condition, the "N" type semiconductor substrate 24forms one side of a capacitor plate, and the first conductivity layer 18forms the other plate of the capacitor. The insulating layers, 20 and22, form the dielectric between the plates. The result is a capacitorhaving a measurable capacitance, C_(o). When small voltages are appliedbetween conductivity layer 18 and conductivity layer 26, it has beenfound that the capacitance of the cell varies with voltage. This changeof capacitance results primarily from a depletion or accumulation ofcarriers in that portion of the "N" type substrate 24 closest to thesilicon dioxide layer. Depletion for example is effected by the presenceon conductivity layer 18 of a potential negative with respect to layer24. The larger the potential difference between the conductivity layerand the substrate, the greater the depth of the depletion layer in the"N" type semiconductor substrate 24. This effect is frequency dependentbecause of the formation of an inversion layer at low frequencies. Sincethe depletion layer acts like a dielectric insulator, the greater thepotential difference, the greater the distance between the effectiveplates of the capacitor formed between the conductivity layer 18 and theinterface between the depleted and non-depleted portions of the N-typesubstrate 24. Thus, as the voltage applied to layer 18 increasesnegatively relative to the substrate layer 24, the capacitance of thecell decreases because the effective distance between the plates of thecapacitor, the cross-sectional area remaining constant, increases. Thereresults a curve relating capacitance as a function of voltage which, ifthe voltage excursions are not too large, does not exhibit hysteresis.

If the potential applied to layer 18 increases positively substantiallywith respect to the substrate 24, there results a shift of thecapacitance as a function of voltage curve along the voltage axis. Thischange in characteristic results from the accumulation and retention ofnegative charge at substantially the interface between the dielectricinsulating layer 20 and the insulating layer 22. In the MNOS device,this accumulation of negative charge results from the differentmagnitudes of current in the oxide and nitride layers. In the preferredembodiment, using the forward shift mode, the accumulation of chargeresults primarily from tunneling, by charge carriers in layer 24,through the silicon dioxide layer into traps present in the dielectricinsulating nitride layer and substantially at the interface between thetwo dielectrics. Significantly, when the potential applied between layer18 and substrate 24 is removed, the charge at the oxide-dielectricinterface 35 remains trapped and there results a capacitor cell in whichthere is accumulated negative charge at the oxide-dielectric interface.

The result is a hysteresis phenomena, which is illustrated schematicallyin FIG. 4 for the preferred embodiment, an MNOS capacitor cell operatingin the forward mode and formed on an N-type silicon substrate 24.Referring to FIG. 4, after a high positive voltage has been applied, thevoltage-capacitance curve describing the capacitor cell is shifted tothe right and corresponds to curve 38. If the voltage is then reducedand even made negative, the capacitance follows that portion 38 of thehysteresis loop. If the potential is made sufficiently negative, thequantity, and in the preferred embodiment, the polarity of the chargetrapped at the interface changes and the voltage-capacitance curvedescribing the cell shifts to the left, curve 36. If thereafter asufficiently high positive potential voltage is placed across thecapacitor cell, the voltage-capacitance curve again shifts to the rightand again follows portion 38 of the hysteresis loop.

The resulting hysteresis loop makes the capacitor array a potentialbuilding block for forming a semiconductor memory. Thus a high positivewriting voltage, corresponding to a first state of stored charge couldrepresent a binary "0", and a high negative writing voltage,corresponding to a second state of stored charge could represent abinary "1". In the preferred embodiment, the first state corresponds toa stored negative charge and the second state corresponds to a storedpositive charge.

Thus according to the theory presented so far, zeros could be written byapplying a high positive voltage across the cell and ones could bewritten by applying a large negative voltage across the cell. Inpractice, however, it is difficult to obtain high writing speeds withoutsome further modification of the capacitor cell because, as discussed indetail below, it takes a relatively long time to change the quantity ofcharge in the depletion direction with stored negative charge at thedielectric-oxide interface.

Using the preferred embodiment as an example, when the negative charge,stored at the dielectric-oxide interface is changed in the depletiondirection by applying a high negative potential, the capacitor cell canbe viewed as two capacitors in series, a first capacitor formed acrossthe dielectric insulating layers between the high conductivity layer 18and the substrate-oxide interface, and a second capacitor formed betweenthe substrate-oxide interface and the boundary between the depleted andundepleted portions of substrate 24. There results a series connectionof two capacitors which acts like a voltage divider to an appliedpotential. In practice, the thickness of the depletion layer is muchgreater than the thickness of the dielectric layer and hence thecapacitance associated with the dielectric layer is much greater thanthe capacitance associated with the depletion layer. Therefore thenegative voltage applied between layers 18 and 26 appears primarilyacross the substrate depletion layer, its smaller capacitance actinglike a larger impedance. The insulating dielectric layers thus see arelatively small potential and therefore the currents flowing throughthe dielectric are negligible. As a result, no charging occurs untilbulk generation builds an inversion layer thereby putting the appliedvoltage across the dielectric layer.

This limitation upon the time required to write is removed, according tothe invention, by doping layer 24 so that it cannot sustain a highvoltage across the depletion layer. The result is a breakdown of thelayer due to avalanche breakdown at a relatively low voltage, theavalanche breakdown voltage, generally comparable to the write voltagein the other direction.

Thus for an applied potential greater than the avalanche voltage oflayer 24, a portion of the applied potential equal to the avalanchebreakdown voltage will fall primarily across the depletion layer whilethat portion of the applied potential greater than the avalanchebreakdown voltage will fall across the dielectric insulating layers.

Layer 24 is preferably uniformly doped, however it can also benon-uniformly doped. In the latter instance, that portion of the layerclosest to the silicon dioxide layer has a lighter than 37 normal"doping whereas that portion further from the oxide layer has a heavy orhigh doping. The thickness of the lightly doped layer is preferablycomparable to the depletion layer at avalanche breakdown voltage.Non-uniform doping may be useful because the change in the capacitanceas a function of voltage (the "flat-band" region of the hysteresis loop)is more abrupt and therefore provides, as will be seen later, a moreeasily recognizable "read" signal.

In a working memory, the write voltage to cause charge storage may betypically 30 volts. An optimum avalanche breakdown voltage would becomparable to this write voltage and is preferably chosen to be equal tothe write voltage, 30 volts, although it may be as low as 6 volts orhigher than 50 volts or more. With these values fixed, a typical set ofoperating parameters would be as follows:

Referring to FIG. 5, to write a "zero" in a selected cell, for examplecell 10a, of the memory without disturbing the remaining cells, apotential of V_(W0), equal to 30 volts, is applied to the word line 12aof the selected cell and the digit or bit line 14a of the selected cellis grounded. This results in trapping a negative charge at thedielectric insulator-oxide interface of the selected cell of thecapacitor memory. The unselected word lines are grounded and theremaining digit lines are set at +30 volts. The unselected cells thussee either a potential of zero or -30 volts. In either instance there issubstantially no effect on the charge stored in these cells.

Referring to FIG. 6, a "one" is written at a selected cell 10a byapplying a potential V_(Wl) =-30 volts to the word line 12acorresponding to each selected cell and a potential V_(D1) =+30 volts tothe digit or bit line 14a corresponding to the selected cell. All of theremaining digit and bit lines are grounded. As a result, a negative 60volts is placed across the selected cell and a potential of -30 volts orzero is applied to each of the unselected capacitor cells. A zeropotential across the capacitor cell does not effect the stored chargeand does not disturb the cell. A potential of -30 volts across a cellalso does not disturb the cell since the bulk of that voltage willappear across the "depletion layer" capacitance and only a small portionacross the dielectric layers. Thus, the tendency to change the chargestored or trapped in the capacitor cell is negligible. The potential of-60 volts across the selected cell however is sufficient to quicklychange the charge stored in the capacitor cell. Thirty of the appliedsixty volts is taken up in avalanche breakdown and the remaining 30volts appears across the dielectric layers to effectively and quicklychange the state of the capacitor. As a result, a large number of writeoperations in the depletion direction can take place at very high speed,without disturbing other cells in the capacitor memory. The typicalwrite speed in either direction according to the invention is onemicrosecond or less.

While writing of only one cell has been described, any selected portionof a memory may be written, in one cycle, so long as the potentialacross the unselected cell, for the values chosen in this embodiment, iszero or -30 volts. In other words, the unselected cells should not bedisturbed.

READ OPERATION

It has been previously suggested, that one cell of a capacitor memoryarray could be read nondestructively by measuring the capacitance of thecell. The capacitance, it is suggested, is measured by placing a smallAC voltage signal across the cell and measuring the resulting current.Such measurements of capacitance are impractical in large arrays becauseof uncontrollable parasitic, coupling and other capacitances inherent ina large array. These uncontrollable capacitances generally mask thecapacitance to be measured and make the measurement of the capacitanceof a single capacitor cell exceedingly difficult and time consuming.

Referring to FIG. 4, according to the invention, an alternate method ofreliably and quickly determining the state of the capacitor cell uses asignal which varies across one of the "flat-band" portions 46, 48 of thehysteresis loop describing the cell. This varying signal is appliedacross the capacitor cell to be read. As a consequence, it is thepresence or absence of a change of capacitance which determines thestate of the capacitor cell. The need to measure the capacitance of thecell is thus eliminated. Since the parasitic and coupling capacitancesare linear elements (or constant capacitances) they do not contribute tothe measurement of a change of capacitance and for that measurement donot reduce the signal to noise ratio of the system.

Preferably, the variable signal is a ramp having a constant slope andhaving a duration much less than the resistance-capacitance timeconstant of the components of the read circuit. Since the capacitor actsas a voltage differentiator, the current passing through the capacitor,when the voltage is a ramp, is proportional to capacitance and thereforethe output current (or voltage V_(o) in the circuit arrangement shown inFIG. 1) is proportional to the capacitance of the system as a functionof voltage. Since the amplitude range of the variable voltage includesone "flat-band" voltage portion of the hysteresis curve, either portion46 or 48, the profile of the voltage output, V_(o) versus time acrosssmall resistor 50 in series with the selected capacitor cell, will, bythe presence or absence of a sudden change of voltage, indicate theexistence or absence of a change in capacitance and therefore whetherthe capacitor is on one or the other leg of the hyteresis curve. Thedetection problem is therefore greatly simplified since only a relativechange in voltage or current (which are, in the preferred embodiment,proportional to capacitance) must be identified; the precise value ofthe voltage or current is not important. This technique is particularlyuseful because as noted above, the other capacitances in the system,which tend to hide the true capacitance of the capacitor cell, areconstant.

During the read operation, the word and digit or bit lines of the cellswhich are not read are grounded and do not interfere with thecapacitance reading of the selected cell. Furthermore neither theselected nor the unselected cells are "disturbed" by the read operationbecause the magnitude of the read voltage applied to those cells duringthe read operation is not sufficient to change the state of the cellsand also because the applied voltage is preferably varied in thedirection of depletion.

A preferred embodiment for obtaining an output voltage which isproportional to the current passing through a capacitor cell is shown inFIG. 1. A read voltage V_(R) is connected to the word line of thecapacitor cells being read. At the same time, the other word lines areconnected to ground. The read voltage in the preferred embodiment is avoltage ramp having a time duration of five microseconds or less and avoltage range of from three to ten volts in magnitude and originatingfrom -10 to +10 volts depending upon the location of the flat-bands andthe method used for signal discrimination. The digit or bit linescorresponding to the selected cells are connected to ground throughsmall resistors 50a, 50b, 50c, which may be, for example, 20,000 ohms.The voltage V_(o) developed across the resistors 50 is essentiallyproportional to the current through and hence the capacitance of thecorresponding capacitor cell. The remaining word and digit lines areconnected directly to ground. A high gain operational amplifier (notshown) is provided to amplify the output voltage V_(o).

The output voltage versus time waveform is then examined for an abruptchange in voltage corresponding to a "flat-band" portion. For example,if the voltage ramp traverses the range ΔV (FIG. 4), then output V_(o)will display a shift in voltage if the cell is in a state correspondingto a capacitance of flat-band 46 and will not display a voltage shiftfor a capacitance state corresponding to flat-band 48. A voltage rampcorresponding to the other "flat-band" portion 48 could also be used.

FABRICATION OF THE CAPACITOR ARRAY

A capacitor array operating in accordance with the preferred embodimentof the invention can be fabricated in several ways.

Air Isolation

According to the preferred embodiment of the invention, shown in FIG. 3,the array is fabricated as follows. Starting with a P-type, (100)orientation, 1 ohm-cm silicon substrate 31 (or a thin layer of intrinsicsilicon substrate on sapphire), the substrate is cleaned by a standardperoxide cleaning procedure as is known in the art, and an arsenosilicafilm is spun onto the wafer. A shallow arsenic N+ diffusion is performedby annealling at 1050° C. for 20 minutes. This gives a junction depth of0.2 microns. The sheet resistance of the diffused layer 30 is about 40ohms/square. This diffusion layer will form the digit or bit lines.

The oxides which were formed during the N+ diffusion are removed byanother peroxide clean and an N-type phosphorous doped epitaxial layer24 is grown on the substrate. The epitaxial layer is 1.5 microns thickand has a doping, N_(o), equal to 1.0×10¹⁶ to provide an avalanchebreakdown voltage of about 30 volts.

An N+ diffusion is now made into those areas of the N-type silicon whichwill underlie metal connection to the digit line outside of the array.This step provides good ohmic contact between the metal connection andthe underlying N-type silicon. After a standard peroxide clean, athermal oxide is grown on the chip in an oxidizing atmosphere at 1000°C. for 3 hours. The thickness of the oxide is about 900 Angstroms.Contact cuts are etched photolithographically in the oxide and thephotoresist is left on the surface for the next step. A plasma etch toremove 1000 to 2000 Angstroms of silicon in the contact cut is thenmade. A standard phosphorous predeposition is then performed from aphosphorous doped glass source which is thermally deposited on the chip.

A masking nitride layer, about 800 Angstroms thick, is then deposited onthe N-type epitaxial layer. This nitride is deposited at a highertemperature, 850° C., than the memory nitride which will be deposited ata later stage in the process. During deposition of the masking nitride,the ammonia to silane ratio is approximately 100 to 1.

The N-type silicon mesa lines, that is, the columns of the array aredefined as follows. The nitride surface is etched using a photomask toform nitride pads on the silicon substrate. An anisotropic etch, usingpotassium hydroxide on the silicon substrate is then performed using thenitride as a mask to the etchant. The etch reaches down to the P-typesubstrate and leaves sloped sidewalls at an angle of 65° to the plane ofthe P-type substrate, surrounding the mesas. The sloped sidewalls areespecially useful for obtaining good metal step coverage on the mesawalls. A thermal oxidation of the exposed silicon surface is thenperformed at 920° C. for 2 hours in oxygen and water to leave a 4000Angstroms thick oxide layer in the cut (the masking nitride protects themesas). This is the field oxide 34 which appears everywhere except ontop of the mesas. The nitride mask is then stripped by applying a 10 to1 solution of water to hydrofluoric acid for 1 minute and washing for 20minutes in phosphoric acid.

The memory oxide and nitride are then grown on the silicon mesas. Thebare silicon on the mesa is cleaned using a standard peroxide cleanfollowed by a 30 second rinse in 10 to 1, water to hydrofluoric acidsolution. The memory oxide 22 is grown in one of two alternate waysdepending upon whether the forward shift mode or the reverse shift modeis being used. In the reverse shift mode, the surface is oxidized in anoxidizing atmosphere for 30 minutes at 800° C. to obtain an oxidethickness of about 40 Angstroms. In the forward shift mode the freshlyetched silicon surface is used by itself. A thermal oxide grown in a0.1% oxygen in nitrogen mixture at 900° C. for 10 minutes may also besuitable.

The silicon nitride layer 20 is then grown on the memory oxide 22. Ifthe reverse shift mode is used, a conductive nitride is deposited at700° C. with a current density of approximately 10 amperes per squarecentimeter at a nitride electric field of 4.8×10⁶ volts/cm. Thisprovides a write time of approximately 100 nanoseconds at 30 volts and anitride thickness of approximately 500 Angstroms. In the forward shiftmode, a less conductive nitride is deposited at 700° C. with a currentdensity of approximately 10⁻⁵ amperes per square centimeter at a nitrideelectric field of 4.8×10⁶ volts/cm. A nitride thickness of 500 Angstromsis also used in this operating mode. The memory nitride is removed fromareas other than the actual array, that is, areas outside the regionsdefined by the row and column intersections, by using a photomask andetching. The nitride is also removed at periodically spaced points alongthe silicon mesa tops which will later be metallized.

An aluminum silicon copper layer, 0.45 micron thick, is now laid down.The silicon substrate is not heated during the metal deposition. Themetal is photoetched to form metal rows of the memory array and themetal lines 28 are extended to bonding pads away from the actual array.

A 0.8 micron thick layer of phosphorous doped silicon dioxide isdeposited by chemical vapor deposition from silane and oxygen. The oxideis photoetched to provide cuts through the deposited oxide to thebonding pads, and at specified points along each N-type silicon mesa.Generally, the cuts are made about once every 100 devices along thecolumns. A second level metal, aluminum, is then deposited andphotoetched to again delineate the bonding pads. Also, metal rows equalin width and running parallel to and directly over the N-type siliconmesa tops are thereby defined.

This structure provides contact to the N-type silicon mesas at aboutevery 100 array intersections. This reduces series resistance along theN-type silicon columns to any device to less than about 2000 ohms.

The array is then sintered at 420° C. and the oxide on the back of thewafer is removed by etching, the front being protected by a mask.

Summarizing the results of this preferred fabrication technique, typicalpreferred thicknesses for the various layers are as follows:

N+ layer (0.0008 ohm-cm)--0.2 microns

N epitaxial layer (0.6 ohm-cm)--1.5 microns

Silicon dioxide layer--20 Angstroms

Silicon nitride layer--500 Angstroms

Aluminum Metal Strip--4,500 Angstroms

Field Oxide--4,000 Angstroms

The N-type epitaxial layer may be more lightly doped. The thickness ofthe lightly doped N epitaxial layer (about 1-2 ohm-cm) is preferablyabout 0.4 micron. In this circumstance the thickness of the N epitaxiallayer, not its doping level, primarily determines the potential at whichavalanche breakdown occurs.

Flip Technique

While the preferred fabrication of the capacitor memory array has beendescribed, other methods and structures may be used to great advantage.A particularly preferred alternate structure, because it replaces thehigh conductivity N+ layer with a metal conductor, is the "fliptechnique" (FIG. 7). The starting wafer 60 is an N+ type siliconsubstrate having a (100) orientation, a thickness of about 8 mils, and adoping concentration greater than 5×10¹⁸ /cm³. The preferred dopant isarsenic or antimony in order to reduce out diffusion during subsequentprocessing. A 7 micron N-type epitaxial layer 62 having a conductivityof approximately 0.5 ohm-cm is grown on the N+ substrate.

A refractory metal, such as platinum or tungsten is then deposited onthe epitaxial layer. The layer 64 is about 2000 Angstroms thick. If themetal is not stable with respect to the reaction with silicon nitride orsilicon up to 1000° C., it should be reacted to form a stable silicidewith the silicon underlying the metal layer. The silicide should have aresistivity less than 50 micro ohm-cm and should have a layer thicknessof about 2000 Angstroms. Platinum silicide may be suitable for thispurpose.

Next, grooves 66 about 2 microns deep are photoetched into the wafer.These grooves will provide isolation between the columns of the array.

An 800 Angstrom mask 68 of silicon nitride is then deposited on thewafer followed by a 1 micron thick layer 70 of deposited silicondioxide. Next, about 200 microns of polycrystalline silicon 72 aredeposited at 900° C.

An electrochemical etch is performed to remove the N+ startingsubstrate. This is a preferential etch which stops at the relativelylowly doped N type epitaxial layer. The etch is performed under thefollowing conditions: A 10 volt potential is applied between the anodeand cathode, the electrolyte is 5% aqueous hydrofluoric acid at a bathtemperature of 18° C. The cathode is platinum gauze (13×13 cm) and thecathode is parallel to the wafer surface and is spaced about 5centimeters away from the surface. The etch is performed in completedarkness. The wafers are prepared for the electrochemical etch byetching in hydrofluoric (48%) and nitric (65%) acids (1 to 10 ratio) toremove work damage. Contact between the anode and the silicon is made bypressing a platinum strip (20×3 mms) against the silicon wafer near itsedge using a perspex clamp. The slice including the contact iscompletely immersed in the electrolyte. If the silicon anode current isto be measured, the platinum strip is covered with an apiezon wax.

After the electrochemical etch, a very thin N+ layer (less than 1micron) and a brown transition layer remain. The first 5 microns of theremaining 7 microns single crystal layer are then removed by means of achemical etch. The composition of this etch is 50 millimeters ofhydrofluoric acid (48%), 50 millimeters of acetic acid (Merck 99%minimum purity), and 200 milligrams potassium permanganate (Merck 99%minimum purity). The etch rate for this composition is approximately 0.2microns per minute at 18° C. The etch is continued until the nitride ontop of the nitride/oxide isolation walls is exposed.

A contact cut and N+ diffusion are then performed as outlined inconnection with the air isolation process in order to ensure properohmic contact to the metal which will connect to the N-type siliconcolumns. A memory oxide 74 and nitride 76 are then grown and photoetchedas described in the air isolation procedure, and the metal strips 78 arethen deposited and etched as described in the air isolation process.

Other Structures

Another desirable structure for an MNOS capacitor array is similar tothe preferred embodiment described above, but in which the air isolationgap between cells is filled with thermally grown silicon dioxide. Atypical structure is shown in FIG. 8 which is constructed in a mannersimilar to that of the air isolation device of FIG. 3. In thefabrication of this device, after the N-type epitaxial layer 80 isgrown, a masking nitride is deposited and etched to form the digit orbit line pattern. X-ray lithography is used to form a 0.2 micron slot 82between digit lines. Then, using the photoresist plus the nitride layerused to form the 0.2 micron slots as a mask, an amorphous layer isformed between the digit lines by ion implanting nitrogen down to the Psubstrate 86 (or sapphire substrate). The photoresist is removed and theamorphous silicon is etched to form a 0.2 micron wide slot which extendsdown to the P substrate (or sapphire substrate). Using the nitride fromthe previous step as an oxidation mask, the walls of the slot areoxidized until the top of the slot is nearly filled with oxide 88. Themasking nitride is then removed and the array is completed by layingdown the oxide 90 and nitride 92 layers and the metal word lines 94 asdescribed previously.

A junction isolation technique, making use of back biased junctions toseparate adjacent capacitor cells, is shown in cross-section in FIG. 9.Its fabrication is similar to that of the other devices describedpreviously. The capacitor cell comprises metal strips 100 on top of asilicon nitride layer 102 and a silicon dioxide layer 104. The N-typeregions 106 adjacent the silicon dioxide layer 104 and the N+ type digitor bit lines 108 adjacent the N-type region complete the capacitor cell.The cells are separated by P-type epitaxial layers 110 and the P-typesubstrate 112 which are back biased at the PN junctions. The field oxide114 further isolates the cells from one another.

Another isolation technique (FIG. 10), called amorphous siliconisolation, uses ion implantation of an electrically inactive material insilicon (e.g. Neon) to create amorphous silicon regions 118, which havea high bulk resistivity, between digit lines to achieve a planar siliconsurface in the final array. The only restriction on this technique isthat highly doped silicon which is found in the buried N+ layer 120,when amorphous, does not possess sufficiently high resistivity forelectrical isolation. The remaining structure, the P-type substrate 122,the nitride 124 and oxide 126 layers, and the metal strips 128 arefabricated as described previously.

Available photolithographic techniques make possible capacitor cellsspaced on 0.2 mil centers. Using the avalanche breakdown and readingtechniques described above, read speeds of five microseconds and writespeeds of 200 manoseconds have been achieved in a small array.

The invention has been described in connection with a structureconstructed using an N-type substrate to operate in the forward shiftmode. Other embodiments of the invention, including those wherein theinvention operates in the reverse mode and/or wherein a P-type substrateis used will occur to those skilled in the art and are within thefollowing claims.

What is claimed is:
 1. A capacitor memory array comprisinga plurality ofisolated capacitor cells arranged in a rectilinear pattern, eachcapacitor cell being described by a voltage versus capacitancerelationship which shifts along a voltage axis under the effect ofapplied potentials, each capacitor cell comprisinga plurality ofmaterial layers, the layers including at least a first high conductivitylayer, a first dielectric insulating layer, a second dielectricinsulating layer, a doped semiconductor substrate, and a second highconductivity layer, and said layers being arranged with said firstconductivity layer overlying said first dielectric insulating layer, thefirst dielectric insulating layer overlying the second dielectricinsulating layer, the second dielectric insulating layer overlying thedoped substrate, and the doped substrate overlying the secondconductivity layer, a first plurality of interconnection paths, eachpath interconnecting a group of said first conductivity layers to formisolated first conductivity paths, a second plurality of interconnectionpaths, each second path interconnecting a group of said second highconductivity layers to form isolated second conductivity paths, one eachof said first and second conductivity paths uniquely identifying at acrossover position one capacitor cell of said memory array, saidsubstrate having a doping concentration in a region near said seconddielectric insulating layer of between 4×10¹⁵ and 1×10¹⁷ impurity atomsper cubic centimeter, said doping concentration having a distributionwhich is uniform in said substrate, and means for selectively applyingan avalanching potential difference between first and second highconductivity layers for producing avalanche breakdown across selectedcell substrate portions adjacent said second dielectric layer.
 2. Acapacitor memory array comprisinga plurality of isolated capacitor cellsarranged in a rectilinear pattern, each capacitor cell being describedby a voltage versus capacitance relationship which shifts along avoltage axis under the effect of applied potentials, each capacitor cellcomprisinga plurality of material layers, the layers including at leasta first high conductivity layer, a first dielectric insulating layer, asecond dielectric insulating layer, a doped semiconductor substrate, anda second high conductivity layer, and said layers being arranged withsaid first conductivity layer overlying said first dielectric insulatinglayer, the first dielectric insulating layer overlying the seconddielectric insulating layer, the second dielectric insulating layeroverlying the doped substrate, and the doped substrate overlying thesecond conductivity layer, a first plurality of interconnection paths,each path interconnecting a group of said first conductivity layers toform isolated first conductivity paths, a second plurality ofinterconnection paths, each second path interconnecting a group of saidsecond high conductivity layers to form isolated second conductivitypaths, one each of said first and second conductivity paths uniquelyidentifying at a crossover position one capacitor cell of said memoryarray, said substrate having a doping concentration in a region nearsaid second dielectric insulating layer of between 4×10¹⁵ and 1×10¹⁷impurity atoms per cubic centimeter, said doped substrate having auniform conductivity type, and the cells associated with one second pathbeing isolated from cells associated with the other remaining secondpaths by a substrate contacting amorphous silicon layer, and means forselectively applying an avalanching potential difference between firstand second high conductivity layers for producing avalanche breakdownacross selected cell substrate portions adjacent said second dielectriclayer.
 3. A capacitor memory array comprisinga plurality of isolatedcapacitor cells arranged in a rectilinear pattern, each capacitor cellbeing described by a voltage versus capacitance relationship whichshifts along a voltage axis under the effect of applied potentials, eachcapacitor cell comprisinga plurality of material layers, the layersincluding at least a first high conductivity layer, a first dielectricinsulating layer, a second dielectric insulating layer, a dopedsemiconductor substrate, and a second high conductivity layer, and saidlayers being arranged with said first conductivity layer overlying saidfirst dielectric insulating layer, the first dielectric insulating layeroverlying the second dielectric insulating layer, the second dielectricinsulating layer overlying the doped substrate, and the doped substrateoverlying the second conductivity layer, a first plurality ofinterconnection paths, each path interconnecting a group of said firstconductivity layers to form isolated first conductivity paths, a secondplurality of interconnection paths, each second path interconnecting agroup of said second high conductivity layers to form isolated secondconductivity paths, one each of said first and second conductivity pathsuniquely identifying at a crossover position one capacitor cell of saidmemory array, said substrate having a doping concentration in a regionnear said second dielectric insulating layer of between 4×10¹⁵ and1×10¹⁷ impurity atoms per cubic centimeter, said doped substrate havinga uniform conductivity type and the cells associated with one secondpath being isolated from cells associated with the other remainingsecond paths by a substrate contacting silicon dioxide barrier, andmeans for selectively applying an avalanching potential differencebetween first and second high conductivity layers for producingavalanche breakdown aross selected cell substrate portions adjacent saidsecond dielectric layer.
 4. In a capacitor memory array comprisingaplurality of isolated capacitor cells arranged in a rectilinear pattern,each capacitor cell exhibiting a measurable hysteresis characteristicunder applied potentials, each capacitor cell comprisinga plurality ofmaterial layers, the layers including at least a first high conductivitylayer, a first dielectric insulating layer, a second dielectricinsulating layer, a doped semiconductor substrate, and a second highconductivity layer, and said layers being arranged with said firstconductivity layer overlying said first dielectric insulating layer, thefirst dielectric insulating layer overlying said second dielectricinsulating layer, the second dielectric layer overlying said dopedsubstrate, and the doped substrate overlying said second conductivitylayer, a first plurality of interconnection paths, each pathinterconnecting a group of said first conductivity layers to formisolated first conductivity paths, a second plurality of interconnectionpaths, each second path interconnecting a group of said second highconductivity layers to form isolated second conductivity paths, and oneeach of said first and second conductivity paths uniquely identifying ata crossover position one capacitor cell of said memory array, theimprovement comprising said substrate being uniformly doped to provideavalanche breakdown across a depletion region of said substrate at apotential between 6 and 50 volts, and means for selectively applying anavalanching potential difference across said first and secondconductivity layers for producing said avalanche breakdown across thedepletion region of selected cells adjacent said second dielectriclayer.
 5. The capacitor memory array of claim 4 wherein said substratehas a thickness comparable to a maximum depletion layer thickness forsaid capacitor memory cells.
 6. In a metal-nitride-oxide-siliconcapacitor memory comprisinga plurality of isolated capacitor cellsarranged in a rectilinear pattern, each cell comprising a plurality ofmaterial layers arranged in sequence, said layers including a conductivemetal layer, an insulating silicon nitride layer, an insulating silicondioxide layer, a doped silicon substrate layer, and a high conductivitylayer, the metal layer overlying the nitride layer, the nitride layeroverlying the dioxide layer, the dioxide layer overlying the substratelayer and the substrate in contact with the conductivity layer, a firstplurality of interconnection paths, each path interconnecting a group ofsaid metal layers to form first conductivity paths, a second pluralityof interconnection paths, each second path interconnecting a group ofsaid second high conductivity layers to form second conductivity paths,each pair of first and second conductivity paths uniquely identifying ata crossover position one cell, and said oxide layer having a thicknessless than about 50 Angstroms, the improvement comprising said substratebeing uniformly doped to provide a low voltage avalanche breakdownacross a depletion layer at a potential less than about 50 and greaterthan about 6 volts, and means for selectively applying an avalanchingpotential difference across said conductive metal layer and said highconductivity layer for producing said avalanche breakdown across thedepletion region of selected cells adjacent said dioxide layer.
 7. Themetal-nitride-oxide-silicon capacitor memory of claim 6 in which saidsubstrate has a thickness comparable to a maximum depletion layerthickness for said capacitor memory cells.